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EP4139371B1 - Complexes de titane et de cyclopentadiényle / adamantyl-phosphinimine - Google Patents

Complexes de titane et de cyclopentadiényle / adamantyl-phosphinimine Download PDF

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EP4139371B1
EP4139371B1 EP21721210.9A EP21721210A EP4139371B1 EP 4139371 B1 EP4139371 B1 EP 4139371B1 EP 21721210 A EP21721210 A EP 21721210A EP 4139371 B1 EP4139371 B1 EP 4139371B1
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adamantyl
unsubstituted
substituted
ticl
group
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EP4139371C0 (fr
EP4139371A1 (fr
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Xiaoliang Gao
Janelle SMILEY-WIENS
Cheng FAN
Brian Molloy
P. Scott Chisholm
Charles Carter
James GOETTEL
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Nova Chemicals International SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
    • C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/07—Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+

Definitions

  • the present disclosure relates to new titanium complexes having a cyclopentadienyl type ligand and a phosphinimine ligand bearing an adamantyl (unsubstituted or substituted) moiety and olefin polymerization catalyst systems that employ these complexes.
  • Titanium complexes having a cyclopentadienyl ligand and a phosphinimine ligand is disclosed in U.S. Patent No. 6,063,879 (Stephan et al. , to NOVA Chemicals International S.A.).
  • the present disclosure provides a complex having the formula (PI)(Cp)TiL 2 , wherein:
  • an olefin polymerization catalyst system comprising:
  • the present disclosure provides a process for the polymerization of olefins comprising contacting one or more C 2 to C 10 alpha olefins with an olefin polymerization catalyst system under polymerization conditions; wherein the olefin polymerization catalyst system comprises:
  • the present disclosure provides a complex having the formula: wherein each L is an activatable ligand.
  • the present disclosure provides a complex having the formula: wherein each L is an activatable ligand.
  • the present disclosure provides a complex having the formula: wherein each L is an activatable ligand.
  • an olefin polymerization catalyst system comprising:
  • an olefin polymerization catalyst system comprising:
  • an olefin polymerization catalyst system comprising:
  • the present disclosure provides a process for the polymerization of olefins comprising contacting one or more of ethylene and C 3 to C 10 alpha olefins with an olefin polymerization catalyst system under polymerization conditions; wherein the olefin polymerization catalyst system comprises:
  • the present disclosure provides a process for the polymerization of olefins comprising contacting one or more of ethylene and C 3 to C 10 alpha olefins with an olefin polymerization catalyst system under polymerization conditions; wherein the olefin polymerization catalyst system comprises:
  • the present disclosure provides a process for the polymerization of olefins comprising contacting one or more of ethylene and C 3 to C 10 alpha olefins with an olefin polymerization catalyst system under polymerization conditions; wherein the olefin polymerization catalyst system comprises:
  • an activator consists of a combination of an aluminoxane and an ionic activator (e.g., trityl borate, [Ph 3 C][B(C 6 F 5 ) 4 ]).
  • an ionic activator e.g., trityl borate, [Ph 3 C][B(C 6 F 5 ) 4 ]
  • an activator consists of a combination of an organoaluminum compound and an ionic activator (e.g., trityl borate, [Ph 3 C][B(C 6 F 5 ) 4 ]).
  • an ionic activator e.g., trityl borate, [Ph 3 C][B(C 6 F 5 ) 4 ]
  • unsubstituted means that hydrogen radicals are bonded to the molecular group that is referred to by the term unsubstituted.
  • substituted means that the group referred to by this term possesses one or more moieties that have replaced one or more hydrogen radicals in any position within the group; non-limiting examples of moieties include halogen radicals (F, Cl, Br), an alkyl group, an alkylaryl group, an arylalkyl group, an alkoxy group, an aryl group, an aryloxy group, an amido group, a silyl group or a germanyl group, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, phenyl groups, naphthyl groups, C 1 to C 10 alkyl groups, C 2 to C 10 alkenyl groups, and combinations thereof.
  • hydrocarbyl refers to linear or branched, aliphatic, olefinic, acetylenic and aryl (aromatic) radicals comprising hydrogen and carbon that are deficient by one hydrogen.
  • cyclic hydrocarbyl group connotes hydrocarbyl groups that comprise cyclic moieties and which may have one or more than one cyclic aromatic ring, and/or one or more than one non-aromatic ring.
  • acyclic hydrocarbyl group connotes hydrocarbyl groups that do not have cyclic moieties such as aromatic or non-aromatic ring structures present within them.
  • heteroatom includes any atom other than carbon and hydrogen that can be bound to carbon.
  • heteroatom containing or “heteroatom containing hydrocarbyl group” means that one or more than one non carbon atom(s) may be present in the hydrocarbyl groups.
  • non-carbon atoms that may be present is a heteroatom containing hydrocarbyl group are N, O, S, P and Si as well as halides such as for example Br and metals such as Sn.
  • heteroatom containing hydrocarbyl groups include for example imines, amine moieties, oxide moieties, phosphine moieties, ethers, ketones, heterocyclics, oxazolines, thioethers, and the like.
  • an "alkyl radical” or “alkyl group” includes linear, branched and cyclic paraffin radicals that are deficient by one hydrogen radical; non-limiting examples include methyl (-CH 3 ) and ethyl (-CH 2 CH 3 ) radicals.
  • alkenyl radical or “alkenyl group” refers to linear, branched and cyclic hydrocarbons containing at least one carbon-carbon double bond that is deficient by one hydrogen radical.
  • alkynyl radical or “alkynyl group” refers to linear, branched and cyclic hydrocarbons containing at least one carbon-carbon triple bond that is deficient by one hydrogen radical.
  • aryl group includes phenyl, naphthyl, pyridyl and other radicals whose molecules have an aromatic ring structure; non-limiting examples include naphthylene, phenanthrene and anthracene.
  • alkylaryl is an alkyl group having an aryl group pendant there from; non-limiting examples include benzyl, phenethyl and tolylmethyl.
  • arylalkyl is an aryl group having one or more alkyl groups pendant there from; non-limiting examples include tolyl, xylyl, mesityl and cumyl.
  • alkoxy group is an oxy group having an alkyl group pendant there from; and includes for example a methoxy group, an ethoxy group, an iso-propoxy group, and the like.
  • aryloxy group is an oxy group having an aryl group pendant there from; and includes for example a phenoxy group, and the like.
  • the adamantyl phosphinimine ligand is defined as: where N is a nitrogen atom; P is a phosphorus atom; each R 1 is unsubstituted adamantyl, or substituted adamantyl and R 1' is selected from the group consisting of unsubstituted adamantyl, substituted adamantyl and C 1 to C 6 hydrocarbyl.
  • adamantyl carbon atom frame in either an unsubstituted or a substituted adamantyl moiety, as referred to in the present disclosure is provided below:
  • the term "unsubstituted adamantyl" as used in this disclosure has a narrow meaning - it is restricted to the well-known hydrocarbon cage structure that contains 10 carbon atoms and excludes “substituted” adamantyl.
  • the term unsubstituted adamantyl as used herein excludes cage structures that contain more than 10 carbon atoms and also excludes structures that contain atoms other than carbon and hydrogen atoms.
  • each of the unsubstituted adamantyl groups on the phosphinimine ligand is 1-adamantyl.
  • substituted adamantyl means that the adamantyl has pendant from its 10 carbon atom frame, one or more substituent(s). It will be appreciated by those skilled in the art that there are two isomers of a substituted adamantyl, namely substituted 1-adamantyl (where the substituted adamantyl moiety is bonded from a tertiary carbon atom to the phosphorus atom of the phosphinimine ligand) and substituted 2-adamantyl (where the substituted adamantyl moiety is bonded from a secondary carbon atom to the phosphorus atom of the phosphinimine ligand).
  • each of the substituted adamantyl groups on the phosphinimine ligand is a substituted 1-adamantyl.
  • a substituted adamantyl has one or more hydrocarbyl group substituents.
  • a substituted adamantyl has one or more heteroatom containing hydrocarbyl group substituents.
  • a substituted adamantyl has one or more halide group substituents.
  • a substituted adamantyl has one or more alkyl group substituents.
  • a substituted adamantyl has one or more aryl group substituents.
  • a substituted adamantyl has one or more methyl group substituents.
  • a substituted 1-adamantyl has one or more hydrocarbyl group substituents.
  • a substituted 1-adamantyl has one or more heteroatom containing hydrocarbyl group substituents.
  • a substituted 1-adamantyl has one or more halide group substituents.
  • a substituted 1-adamantyl has one or more alkyl group substituents.
  • a substituted 1-adamantyl has one or more aryl group substituents.
  • a substituted 1-adamantyl has one or more methyl group substituents.
  • a substituted 1-adamantyl has a methyl group substituent at the 3-position and the 5-position.
  • a substituted 1-adamantyl has a methyl group substituent at the 3-position, the 5-position and the 7-position.
  • each R 1 is an unsubstituted adamantyl.
  • each R 1 is a substituted adamantyl.
  • each R 1 is an unsubstituted 1-adamantyl.
  • each R 1 is a substituted 1-adamantyl.
  • each R 1 is a substituted 1-adamantyl having methyl group substituent at the 3-position and the 5-position.
  • each R 1 is a substituted 1-adamantyl having a methyl group substituent at the 3-position, the 5-position and the 7-position.
  • R 1' is an unsubstituted adamantyl.
  • R 1' is a substituted adamantyl.
  • R 1' is an unsubstituted 1-adamantyl.
  • R 1' is a substituted 1-adamantyl.
  • R 1' is a substituted 1-adamantyl having methyl group substituent at the 3-position and the 5-position.
  • R 1' is a substituted 1-adamantyl having a methyl group substituent at the 3-position, the 5-position and the 7-position.
  • R 1' is a C 1 to C 6 hydrocarbyl.
  • the cyclopentadienyl-type ligands comprise a 5-membered carbon ring having delocalized bonding within the ring and bound to the metal, which ring is unsubstituted or may be further substituted (sometimes referred to in a short form as Cp ligands).
  • Cyclopentadienyl-type ligands include unsubstituted cyclopentadienyl, substituted cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted fluorenyl and substituted fluorenyl.
  • An exemplary list of substituents for a cyclopentadienyl-type ligand includes the group consisting of C 1-10 hydrocarbyl radicals (which hydrocarbyl radical may be unsubstituted or further substituted by for example a halide and/or a hydrocarbyl group; for example a suitable substituted C 1-10 hydrocarbyl radical is a pentafluorobenzyl group such as -CH 2 C 6 F 5 ); a C 1-4 alkyl radical; a C 1-8 alkoxy radical; a C 6-10 aryl or aryloxy radical; an amido radical which is unsubstituted or substituted by up to two C 1-8 alkyl radicals; a phosphido radical which is unsubstituted or substituted by up to two C 1-8 alkyl radicals; silyl radicals of the formula -Si-(R)s wherein each R is independently selected from the group consisting of hydrogen, a C 1-8 alkyl
  • the cyclopentadienyl-type ligand is pentamethylcyclopentadienyl.
  • the cyclopentadienyl-type ligand is penta (n-propyl)cyclopentadienyl.
  • the cyclopentadienyl-type ligand is cyclopentadienyl.
  • the cyclopentadienyl-type ligand is tetramethyl(pentafluorobenzyl)cyclopentadienyl, CpMe 4 (CH 2 C 6 F 5 ).
  • the cyclopentadienyl-type ligand is (pentafluorobenzyl)cyclopentadienyl, Cp(CH 2 C 6 F 5 ).
  • the cyclopentadienyl-type ligand is tetramethyl(3,5-tert-butylphenyl)cyclopentadienyl, CpMe 4 (-3,5-t-Bu 2 -C 6 H 3 ).
  • the cyclopentadienyl-type ligand is 1,2,3-trimethyl-4-phenyl-4-hydrocyclopent[b]indolyl.
  • activatable ligand refers to a ligand which may be activated by a cocatalyst (also referred to as an "activator"), to facilitate olefin polymerization.
  • An activatable ligand L may be cleaved from the metal center M of the catalyst via a protonolysis reaction or abstracted from the metal center M by suitable acidic or electrophilic catalyst activator compounds (also known as "co-catalyst” compounds) respectively, examples of which are described below.
  • the activatable ligand L may also be transformed into another ligand which is cleaved or abstracted from the metal center M (e.g., a halide may be converted to an alkyl group).
  • the activatable ligand, L is independently selected from the group consisting of a hydrogen atom; a halogen atom; a C 1-10 hydrocarbyl radical; a C 1-10 alkoxy radical; a C 6-10 aryl oxide radical, each of which said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted by or further substituted by a halogen atom, a C 1-8 alkyl radical, a C 1-8 alkoxy radical, a C 6-10 aryl or aryloxy radical; an amido radical which is unsubstituted or substituted by up to two C 1-8 alkyl radicals; and a phosphido radical which is unsubstituted or substituted by up to two C 1-8 alkyl radicals.
  • Two activatable L ligands may also be joined to one another and form for example, a substituted or unsubstituted diene ligand (e.g., 1,3-diene); or a delocalized heteroatom containing group such as an acetate group.
  • a substituted or unsubstituted diene ligand e.g., 1,3-diene
  • a delocalized heteroatom containing group such as an acetate group.
  • the number of activatable ligands depends upon the valency of the metal and the valency of the activatable ligand.
  • the preferred phosphinimine catalysts are based on group 4 metals in their highest oxidation state (i.e., 4 + ).
  • Particularly suitable activatable ligands are monoanionic such as a halide (e.g., chloride) or a hydrocarbyl (e.g., methyl, benzyl).
  • the metal of the phosphinimine catalyst may not be in the highest oxidation state.
  • a titanium (III) component would contain only one activatable ligand.
  • the activatable ligand, L is methyl
  • the activatable ligand, L is benzyl ("Bn" for short).
  • the activatable ligand, L is chloride
  • the complex is used in combination with at least one activator (or "cocatalyst") to form an active polymerization catalyst system for olefin polymerization.
  • activators i.e., cocatalysts
  • cocatalysts include ionic activator cocatalysts and aluminoxane cocatalysts and may in some embodiments include organoaluminum compounds as cocatalysts.
  • the activator comprises one or more of the following: an aluminoxane compound, an ionic activator, an organoaluminum compound.
  • a hindered phenol may optionally be used in combination with an aluminoxane compound or an organoaluminum compound.
  • the activator is an organoaluminum compound and an ionic activator. In an embodiment of the disclosure the activator is an aluminoxane compound and an ionic activator. In an embodiment of the invention the activator is an ionic activator.
  • the activator is selected from the group consisting of an aluminoxane; an organoaluminum compound; an ionic activator; and mixtures thereof.
  • Aluminoxane also referred to as Alkylaluminoxane
  • the activator used to activate the single site catalyst can be any suitable activator including one or more activators selected from the group consisting of alkylaluminoxanes and ionic activators, optionally together with an alkylating agent.
  • the alkylaluminoxanes are complex aluminum compounds of the formula: R 4 2 Al 1 O(R 4 Al 1 O) m Al 1 R 4 2 , wherein each R 4 is independently selected from the group consisting of C 1-20 hydrocarbyl radicals and m is from 3 to 50.
  • a hindered phenol can be added to the alkylaluminoxane to provide a molar ratio of Al 1 :hindered phenol of from 2:1 to 5:1 when the hindered phenol is present.
  • R 3 of the alkylaluminoxane is a methyl radical and m is from 10 to 40.
  • the alkylaluminoxanes are typically used in substantial molar excess compared to the amount of group 4 transition metal in the single site catalyst.
  • the Al 1 :group 4 transition metal molar ratios are from 5:1 to 10,000:1, such as about 30:1 to 500:1.
  • alkylaluminoxane can serve dual roles as both an alkylator and an activator.
  • an alkylaluminoxane activator is often used in combination with activatable ligands such as halogens.
  • the activator of the present disclosure may be a combination of an alkylating agent (which may also serve as a scavenger) with an activator capable of ionizing the group 4 metal of the single site catalyst (i.e., an ionic activator).
  • an ionic activator capable of ionizing the group 4 metal of the single site catalyst.
  • the activator can be chosen from one or more alkylaluminoxane and/or an ionic activator.
  • the alkylating agent may be selected from the group consisting of (R*) p MgX 2 2-p wherein X 2 is a halide and each R* is independently selected from the group consisting of C 1-10 alkyl radicals and p is 1 or 2; R*Li wherein in R* is as defined previously, (R*) q ZnX 2 2-q wherein R* is as defined previously, X 2 is halogen and q is 1 or 2; (R 4 ) s Al 2 X 2 3-s wherein R* is as defined previously, X 2 is halogen and s is an integer from 1 to 3.
  • R* is a C 1-4 alkyl radical
  • X 2 is chlorine.
  • Commercially available compounds include triethyl aluminum (TEAL), diethyl aluminum chloride (DEAC), dibutyl magnesium ((Bu) 2 Mg) and butyl ethyl magnesium (BuEtMg or BuMgEt).
  • organoaluminum compounds include triethylaluminum, triisobutyl aluminum, tri-n-octylaluminum and diethyl aluminum ethoxide.
  • the ionic activator may be selected from the group consisting of: (i) compounds of the formula [R 5 ] + [B(R 6 ) 4 ] - wherein B is a boron atom, R 5 is a cyclic C 5-7 aromatic cation or a triphenyl methyl cation and each R 6 is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted with from 3 to 5 substituents selected from the group consisting of a fluorine atom, a C 1-4 alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom; and a silyl radical of the formula --Si--(R 7 ) 3 ; wherein each R 7 is independently selected from the group consisting of a hydrogen atom and a C 1-4 alkyl radical; (ii) compounds of the formula [(R 8 ) t ZH] + [B(R 6 ) 4 ] - wherein B
  • R 6 is a pentafluorophenyl radical
  • R 5 is a triphenylmethyl cation
  • Z is a nitrogen atom
  • R 8 is a C 1-4 alkyl radical or one R 8 taken together with a nitrogen atom forms an anilinium radical (e.g., PhR 8 2 NH + , which is substituted by two R 8 radicals such as for example two C 1-4 alkyl radicals).
  • Examples of compounds capable of ionizing the single site catalyst include the following compounds: triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra (o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-
  • activators which are capable of ionizing the group 4 metal of the single site catalyst include: N,N-dimethylaniliniumtetrakispentafluorophenyl borate ("[Me 2 NHPh][B(C 6 F 5 ) 4 ]”); triphenylmethylium tetrakispentafluorophenyl borate ("[Ph 3 C][B(C 6 F 5 ) 4 ]”); and trispentafluorophenyl boron and MAO (methylaluminoxane) and MMAO (modified methylaluminoxane).
  • the ionic activators compounds may be used in amounts which provide a molar ratio of group 4 transition metal to boron that will be from 1:1 to 1:6.
  • mixtures of alkylaluminoxanes and ionic activators can be used as activators in the polymerization catalyst.
  • Non-limiting example of hindered phenols which may be employed in some embodiments of the present invention include butylated phenolic antioxidants, butylated hydroxytoluene, 2,6-di-tertiarybutyl-4-ethyl phenol, 4,4'-methylenebis (2,6-di-tertiary-butylphenol), 1,3, 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate.
  • butylated phenolic antioxidants butylated hydroxytoluene
  • 2,6-di-tertiarybutyl-4-ethyl phenol 4,4'-methylenebis (2,6-di-tertiary-butylphenol)
  • 1,3, 5-trimethyl-2,4,6-tris (3,5
  • the catalyst precursor, the activator, or the entire catalyst composition may be impregnated onto a solid, inert support, in liquid form such as a solution, dispersion or neat liquid, spray dried, in the form of a prepolymer or formed in-situ during polymerization.
  • the catalyst composition may be impregnated in or deposited on the surface of an inert substrate such as silica, clay, carbon black, polyethylene, polycarbonate porous crosslinked polystyrene, porous crosslinked polypropylene, alumina, thoria, zirconia or magnesium halide (e.g., magnesium dichloride), such that the catalyst composition is between 0.1 and 90 percent by weight of the total weight of the catalyst composition and the support.
  • an inert substrate such as silica, clay, carbon black, polyethylene, polycarbonate porous crosslinked polystyrene, porous crosslinked polypropylene, alumina, thoria, zirconia or magnesium halide (e.g., magnesium dichloride), such that the catalyst composition is between 0.1 and 90 percent by weight of the total weight of the catalyst composition and the support.
  • the catalyst composition may be used for the polymerization of olefins by any suspension, solution, slurry, or gas phase process, using known equipment and reaction conditions, and is not limited to any specific type of reaction system.
  • olefin polymerization temperatures range from about 0°C to about 200°C at atmospheric, subatmospheric, or superatmospheric pressures.
  • Slurry or solution polymerization processes may utilize subatmospheric or superatmospheric pressures and temperatures in the range of about 40°C to about 110°C.
  • a useful liquid phase polymerization reaction system is described in U.S. Patent No. 3,324,095 .
  • Liquid phase reaction systems generally comprise a reactor vessel to which olefin monomer and catalyst composition are added, and which contains a liquid reaction medium for dissolving or suspending the polyolefin.
  • the liquid reaction medium may consist of the bulk liquid monomer or an inert liquid hydrocarbon that is nonreactive under the polymerization conditions employed.
  • an inert liquid hydrocarbon need not function as a solvent for the catalyst composition or the polymer obtained by the process, it usually serves as solvent for the monomers employed in the polymerization.
  • the inert liquid hydrocarbons suitable for this purpose are isopentane, hexane, cyclohexane, heptane, benzene, toluene, and the like.
  • Reactive contact between the olefin monomer and the catalyst composition should be maintained by constant stirring or agitation.
  • the reaction medium containing the olefin polymer product and unreacted olefin monomer is withdrawn from the reactor continuously.
  • the olefin polymer product is separated, and the unreacted olefin monomer and liquid reaction medium are recycled into the reactor.
  • An embodiment of the disclosure is an olefin polymerization process comprising contacting one or more of ethylene and C 3 to C 10 alpha olefins with the olefin polymerization catalyst system described herein under polymerization conditions.
  • An embodiment of the disclosure is an olefin polymerization process comprising contacting one or more of ethylene and C 3 to C 10 alpha olefins with the olefin polymerization catalyst system described herein under solution phase polymerization conditions.
  • An embodiment of the disclosure is an olefin polymerization process comprising contacting ethylene and one or more olefins selected from the group consisting of 1-butene, 1-hexene and 1-octene with the olefin polymerization catalyst system described herein under polymerization conditions.
  • An embodiment of the disclosure is an olefin polymerization process comprising contacting ethylene and one or more olefins selected from the group consisting of 1-butene, 1-hexene and 1-octene with the olefin polymerization catalyst system described herein under solution phase polymerization conditions.
  • pressures may be in the range of 7 to 6895 kPa (1 to 1000 psi), such as 340 to 2760 kPa (50 to 400 psi), for example 689 to 2070 kPa (100 to 300 psi), and temperatures in the range of 30°C to 130°C, for example 65°C to 110°C.
  • Stirred or fluidized bed gas phase reaction systems are particularly useful.
  • a conventional gas phase, fluidized bed process is conducted by passing a stream containing one or more olefin monomers continuously through a fluidized bed reactor under reaction conditions and in the presence of catalyst composition at a velocity sufficient to maintain a bed of solid particles in a suspended condition.
  • a stream containing unreacted monomer is withdrawn from the reactor continuously, compressed, cooled, optionally fully or partially condensed as disclosed in U.S. Patent Nos. 4,588,790 and 5,462,999 , and recycled to the reactor.
  • Product is withdrawn from the reactor and make-up monomer is added to the recycle stream.
  • any gas inert to the catalyst composition and reactants may also be present in the gas stream.
  • Polymerization may be carried out in a single reactor or in two or more reactors in series and is conducted substantially in the absence of catalyst poisons.
  • Organometallic compounds may be employed as scavenging agents for poisons to increase the catalyst activity.
  • scavenging agents are metal alkyls, including aluminum alkyls, such as triisobutylaluminum.
  • Hydrogen or a metal or non-metal hydride may be used as a chain transfer agent in the process. Hydrogen may be used in amounts up to about 10 moles of hydrogen per mole of total monomer feed.
  • Olefin polymers that may be produced according to the disclosure include, but are not limited to, ethylene homopolymers, homopolymers of linear or branched higher alpha-olefins containing 3 to about 20 carbon atoms, and interpolymers of ethylene and such higher alpha-olefins, with densities ranging from about 0.86 to about 0.96.
  • Suitable higher alpha-olefins include, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 3,5,5-trimethyl-1-hexene.
  • Olefin polymers according to the disclosure may also be based on or contain conjugated or non-conjugated dienes, such as linear, branched, or cyclic hydrocarbon dienes having from about 4 to about 20 carbon atoms, for example 4 to 12 carbon atoms.
  • preferred dienes include 1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2-norbornene, 1,7-octadiene, vinyl cyclohexene, dicyclopentadiene, butadiene, isobutylene, isoprene, ethylidene norbornene and the like.
  • Aromatic compounds having vinyl unsaturation such as styrene and substituted styrenes, and polar vinyl monomers such as acrylonitrile, maleic acid esters, vinyl acetate, acrylate esters, methacrylate esters, vinyl trialkyl silanes and the like may be polymerized according to the disclosure as well.
  • Specific olefin polymers that may be made according to the disclosure include, for example, polyethylene, polypropylene, ethylene/propylene rubbers (EPR's), ethylene/propylene/diene terpolymers (EPDM's), polybutadiene, polyisoprene and the like.
  • slurry polymerization processes are widely reported in the patent literature. For example, particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution is described in U.S. Patent No. 3,248,179 .
  • Slurry processes include those employing a loop reactor and those utilizing a single stirred reactor or a plurality of stirred reactors in series, parallel, or combinations thereof.
  • Non-limiting examples of slurry processes include continuous loop or stirred tank processes. Further examples of slurry processes are described in U.S. Patent No. 4,613,484 .
  • Slurry processes are conducted in the presence of a hydrocarbon diluent such as an alkane (including isoalkanes), an aromatic or a cycloalkane.
  • the diluent may also be the alpha olefin comonomer used in copolymerizations.
  • Alkane diluents include propane, butanes, (i.e., normal butane and/or isobutane), pentanes, hexanes, heptanes and octanes.
  • the monomers may be soluble in (or miscible with) the diluent, but the polymer is not (under polymerization conditions).
  • the polymerization temperature can be from about 5°C to about 200°C.
  • the polymerization temperature is less than about 120°C, such as from about 10°C to about 100°C.
  • the reaction temperature is selected so that an ethylene copolymer is produced in the form of solid particles.
  • the reaction pressure is influenced by the choice of diluent and reaction temperature. For example, pressures may range from 15 to 45 atmospheres (about 220 to 660 psi or about 1,500 to about 4,600 kPa) when isobutane is used as diluent to approximately twice that (i.e., from 30 to 90 atmospheres - about 440 to 1,300 psi or about 3,000 to 9,100 kPa) when propane is used (see, for example, U.S. Patent No. 5,684,097 ).
  • the pressure in a slurry process must be kept sufficiently high to keep at least part of the ethylene monomer in the liquid phase.
  • the reaction typically takes place in a jacketed closed loop reactor having an internal stirrer (e.g., an impeller) and at least one settling leg. Catalyst, monomers and diluents are fed to the reactor as liquids or suspensions.
  • the slurry circulates through the reactor and the jacket is used to control the temperature of the reactor. Through a series of let down valves the slurry enters a settling leg and then is let down in pressure to flash the diluent and unreacted monomers and recover the polymer generally in a cyclone. The diluent and unreacted monomers are recovered and recycled back to the reactor.
  • Solution processes for the copolymerization of ethylene and an alpha olefin having from 3 to 12 carbon atoms are well known in the art. These processes are conducted in the presence of an inert hydrocarbon solvent typically a C 5-12 hydrocarbon which may be unsubstituted or substituted by a C 1-4 alkyl group, such as pentane, methyl pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha.
  • an inert hydrocarbon solvent typically a C 5-12 hydrocarbon which may be unsubstituted or substituted by a C 1-4 alkyl group, such as pentane, methyl pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha.
  • An example of a suitable solvent which is commercially available is ISOP
  • a solution polymerization process may use one, two (or more) polymerization reactors.
  • the polymerization temperature in at least one CSTR is from about 80°C to about 280°C (e.g., from about 120°C to 220°C) and a tubular reactor is operated at a slightly higher temperature.
  • Cold feed i.e., chilled solvent and/or monomer
  • the polymerization enthalpy heats the reactor.
  • the polymerization solution which exits in the reactor may be more than 100°C hotter than the reactor feed temperature.
  • Agitation efficiency in the CSTR may be determined by measuring the reactor temperature at several different points. The largest temperature difference (i.e., between the hottest and coldest temperature measurements) is described as the internal temperature gradient for the polymerization reactor.
  • a very well mixed CSTR has a maximum internal temperature gradient of less than 10°C.
  • An example agitator system is described in commonly assigned U.S. Patent No. 6,024,483 .
  • preferred pressures are from about 3450 to 55160 kPa (500 psi to 8,000 psi).
  • the preferred reaction process is a "medium pressure process", which means that the pressure in each reactor is less than about 6,000 psi (about 41,000 kiloPascals or kPa)-for example, from about 1,500 psi to 3,000 psi (about 10,000-21,000 kPa).
  • catalyst can be added to each of the CSTR(s) in order to maintain a high reactor rate.
  • the catalyst used in each CSTR may be the same or different, but it is generally preferable to use the same type of catalyst in each CSTR.
  • at least 60 weight % of the ethylene fed to the CSTR(s) is polymerized to polyethylene in the CSTR(s).
  • at least 70 weight % of the ethylene fed to the CSTR(s) can be polymerized to polyethylene in the CSTR(s).
  • the single site catalyst can be employed in the first CSTR and the Z/N catalyst can be employed in the second CSTR.
  • Z/N Ziegler-Natta
  • a tubular reactor that is connected to the discharge of the at least one CSTR may also be employed. If two CSTR's are used in series, then the tubular reactor receives the discharge from the second CSTR.
  • tubular reactor is meant to convey its conventional meaning: namely a simple tube.
  • the tubular reactor of this disclosure will have a length/diameter (L/D) ratio of at least 10/1.
  • the tubular reactor is not agitated.
  • the tubular reactor can be operated adiabatically.
  • the temperature increase along the length of the tubular reactor may be greater than 3°C (i.e., that the discharge temperature from the tubular reactor is at least 3°C greater than the discharge temperature from the CSTR that feeds the tubular reactor).
  • the tubular reactor may also have feed ports for additional catalyst, cocatalyst, comonomer and/or telomerization agent (such as hydrogen).
  • additional catalyst such as hydrogen
  • cocatalyst such as cocatalyst
  • comonomer such as hydrogen
  • telomerization agent such as hydrogen
  • the total volume of the tubular reactor can be at least 10 volume % of the volume of the at least one CSTR, especially from 30% to 200% (for clarity, if the volume of the CSTR is 1000 liters, then the volume of the tubular reactor is at least 100 liters; for example, from 300 to 2,000 liters).
  • Suitable monomers for copolymerization with ethylene include C 3-12 alpha olefins which are unsubstituted or substituted by up to two C 1-6 alkyl radicals.
  • alpha-olefins are one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene; as well as mixtures thereof.
  • octene-1 is preferred.
  • the monomers are dissolved/dispersed in the solvent either prior to being fed to the first CSTR (or for gaseous monomers the monomer may be fed to the reactor so that it will dissolve in the reaction mixture).
  • the solvent and monomers Prior to mixing, are generally purified to remove potential catalyst poisons such as water, oxygen or other polar impurities.
  • the feedstock purification follows standard practices in the art, e.g., molecular sieves, alumina beds and oxygen removal catalysts are used for the purification of monomers.
  • the solvent itself as well e.g., methyl pentane, cyclohexane, hexane or toluene
  • the catalyst components may be premixed in the solvent for the reaction or fed as separate streams to each reactor.
  • premixing may be desirable to provide a reaction time for the catalyst components prior to entering the first CSTR.
  • in-line mixing is described in the patent literature (most notably U.S. Patent No. 5,589,555, issued Dec. 31, 1996 to DuPont Canada Inc.).
  • the residence time in each reactor will depend on the design and the capacity of the reactor. Generally, the reactors can be operated under conditions to achieve a thorough mixing of the reactants. As previously noted, the polymerization reactors are arranged in series (i.e., with the solution from the at least one CSTR being transferred to the tubular reactor).
  • Chloroform was used as received from Sigma Aldrich. Anhydrous methanol and ethanol were distilled from sodium. Phosphorous chloride, adamantane, aluminum chloride, lithium aluminum hydride, silver trifluoromethane sulfonate, 1-adamantol, trimethylsilyl trifluoromethane sulfonate and cyclopentadienyltitanium trichloride were used as received from Sigma Aldrich. Triethylamine was purchased from Sigma Aldrich and distilled over activated molecular sieves prior to use.
  • Deuterated solvents tetrahydrofuran-ds, toluene-ds
  • Deuterated solvent chloroform-d, dichloromethane-d 2 , toluene-ds
  • NMR spectra were recorded on a Bruker 400 MHz spectrometer ( 1 H: 400.1 MHz, 19 F: 376 MHz, 31 P: 162 MHz).
  • Polymer sample solutions (1 to 2 mg/mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on a wheel for 4 hours at 150°C in an oven.
  • TCB 1,2,4-trichlorobenzene
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • Sample solutions were chromatographed at 140°C on a PL 220 high-temperature chromatography unit equipped with four SHODEX ® columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase with a flow rate of 1.0 mL/minute, with a differential refractive index (DRI) as the concentration detector.
  • BHT was added to the mobile phase at a concentration of 250 ppm to protect the columns from oxidative degradation.
  • the sample injection volume was 200 mL.
  • the raw data were processed with CIRRUS ® GPC software.
  • the columns were calibrated with narrow distribution polystyrene standards.
  • the polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation, as described in the ASTM standard test method D6474.
  • FTIR Fourier Transform Infrared
  • phosphorous chloride 100 g; 728 mmol, was added to adamantane (27 g; 198 mmol) and aluminum chloride (25 g, 187 mmol) with a large stir bar for effective stirring.
  • the solution was stirred overnight at 90°C.
  • the reaction was cooled off and the excess phosphorous chloride was removed via distillation.
  • Degassed chloroform 60 mL was added to form a slurry.
  • the slurry was cooled to 0°C and degassed water (300 mL) was added dropwise with vigorous stirring for 30 minutes.
  • the slurry was filtered and filtrated was separated.
  • the organic layer was collected.
  • the aqueous layer was extracted with dichloromethane.
  • the chloroform and dichloromethane solutions were combined and dried over MgSO 4 .
  • a white solid (27.0 g, 41%) was obtained after volatiles were pumped off.
  • trimethylsilyl trifluoromethane sulfonate (8.5 mL, 46.5 mmol) was added to a solution of bis(1-adamantyl)phosphine (11.75 g, 38.9 mmol) and 1-adamantylacetate (8.30 g, 46.5 mmol) in dichloromethane (100 mL).
  • the reaction was allowed to stir at ambient temperature over 24 hours.
  • Trimethylamine 26 mL, 187 mmol was added dropwise and the reaction was stirred for 30 minutes. The volatiles were removed in vacuo. The residue was slurried in toluene and filtered off a white solid. The solid was slurried in degassed ethanol and filtered.
  • 1,3-dimethyladamantane (10 g, 60.86 mmol) and AlCl 3 (9.5 g, 71 mmol) were weighed into a 150 mL Schlenk flask with a large stir bar.
  • PCl 3 40 mL was added to the flask. The mixture was stirred and was heated to 90°C overnight. An orange slurry produced. The excess PCl 3 was distilled out at 115-120°C.
  • the flask was cooled to room temperature and degassed chloroform (100 mL) was added. The flask was cooled to 0°C, and degassed water (20 mL) was added under nitrogen dropwise from a syringe over about 1 hour.
  • the product from the last reaction was dissolved in THF (150 mL). The solution was cooled to -10°C in a glove box. LiAlH 4 (3.5 g, excess) in THF ( ⁇ 50 mL) was added from a dropping funnel in about 1 hour. The reaction was stirred overnight. The next morning, the temperature was raised to 40°C for 2 hours. The solvent was pumped off. The residue was extracted with pentane (3x100 mL) and the pentane solution was pumped to dryness to give the product, (3,5-Me 2 -1-Ad) 2 PH, as a crystalline solid (8.0 g).
  • Continuous polymerizations were conducted on a continuous polymerization unit (CPU) using cyclohexane as the solvent.
  • the CPU contained a 71.5 mL stirred reactor and was operated between 130 to 190°C for the polymerization experiments.
  • An upstream mixing reactor having a 20 mL volume was operated at 5°C lower than the polymerization reactor. The mixing reactor was used to preheat the ethylene, octene and some of the solvent streams.
  • Catalyst feeds xylene or cyclohexane solutions of the pre-catalyst complex (e.g., Cp(1-Ad 3 PN)TiCl 2 ) and (Ph 3 C)[B(C 6 F 5 ) 4 ] as a catalyst activator and additional solvent were added directly to the polymerization reactor in a continuous process.
  • Additional feeds of MMAO-7 with and without 2,6-di-tert-butyl-4-ethylphenol (BHEB) and solvent were also added to the polymerization unit.
  • MMAO-7 is a commercially available methylaluminoxane that is reported to contain some higher alkyl substituents (C 4 -C 6 ) in addition to methyl substituents. A total continuous flow of 27 mL/min into the polymerization reactor was maintained.
  • Copolymers were made at 1-octene /ethylene weight ratios ranging from 0.15 to 0.5.
  • the ethylene was fed at a 10 wt% ethylene concentration in the polymerization reactor.
  • the CPU system operated at a pressure of 10.5 MPa.
  • the solvent, monomer, and comonomer streams were all purified by the CPU systems before entering the reactor.
  • Copolymer samples were collected at 90 ⁇ 1% ethylene conversion (Q), dried in a vacuum oven, ground, and then analyzed using FTIR (for short-chain branch frequency) and GPC-RI (for molecular weight and distribution).
  • Comparative and new catalysts were used in this example (Example A).
  • the comparative catalyst is Cp(t-Bu 3 PN)TiCl 2 , which is known to be an excellent catalyst for solution polymerization.
  • the new catalyst, Cp(1-Ad 3 PN)TiCl 2 produces polymer molecular weight (MW) independent of the BHEB/AI ratio, which gives consistent products.
  • MW polymer molecular weight independent of the BHEB/AI ratio
  • Polymer molecular weight vs BHEB/AI ratio are tabulated in Table 1 and plotted in Figure 1 .
  • Activity data of the catalyst Cp(1-Ad 3 PN)TiCl 2 and a comparative catalyst Cp(tBu 3 PN)TiCl 2 at 130°C, 140°C and 160°C without the addition of BHEB are tabulated in Table 2 and plotted in Figure 2 .
  • the catalyst Cp(1-Ad 3 PN)TiCl 2 was more active than Cp( t BusPN)TiCl 2 , indicating that the catalyst is less sensitive to trimethyl aluminum.
  • the polymers were made using a continuous solution polymerization process in a CPU unit as already described above; however, in addition to using MAO as a cocatalyst (or scavenger), other organoaluminum compounds, such as triethylaluminum (TEAL), tributylaluminum (TiBAI), tri-n-octyl aluminum (TnOAI), and diethylaluminum ethoxide (Et 2 AlOEt) were also explored, as indicated in Tables 3, 4, and 5. The use of varying levels of a hindered phenol (BHEB) was again explored in these examples.
  • TEAL triethylaluminum
  • TiBAI tributylaluminum
  • TnOAI tri-n-octyl aluminum
  • Et 2 AlOEt diethylaluminum ethoxide
  • titanium complexes which have a cyclopentadienyl type ligand and a phosphinimine ligand bearing an adamantyl (unsubstituted or substituted) moiety.
  • the new complexes are active in the polymerization of ethylene with an alpha olefin.

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Claims (18)

  1. Complexe répondant à la formule (PI) (Cp) TiL2, dans lequel :
    I) PI est un ligand de phosphinimine défini par la formule :
    Figure imgb0035
     où N est un atome d'azote ; P est un atome de phosphore ; chaque R1 est un adamantyle non substitué, ou un adamantyle substitué ; et R1'est choisi dans le groupe constitué d'un adamantyle non substitué, d'un adamantyle substitué et d'un hydrocarbyle en C1 à C6 ;
    II) Cp est un ligand de type cyclopentadiényle comprenant un cycle de carbone à 5 chaînons présentant une liaison délocalisée à l'intérieur du cycle et lié à Ti, lequel cycle est non substitué ou peut être substitué davantage ;
    III) chaque L est un ligand activable ; et
    IV) Ti est le titane.
  2. Complexe selon la revendication 1, dans lequel R1'est un adamantyle non substitué ou un adamantyle substitué.
  3. Complexe selon la revendication 1, dans lequel R1' est un adamantyle non substitué.
  4. Complexe selon l'une quelconque des revendications 1 à 3, dans lequel chaque R1 est un adamantyle non substitué.
  5. Complexe selon la revendication 4, dans lequel R1' et chaque R1 est un 1-adamantyle.
  6. Complexe selon l'une quelconque des revendications 1 à 5, dans lequel Cp est un (pentaméthyl)cyclopentadiényle.
  7. Complexe selon l'une quelconque des revendications 1 à 5, dans lequel Cp est un cyclopentadiényle.
  8. Système de catalyseur de polymérisation d'oléfines comprenant :
    A) un complexe répondant à la formule (PI) (Cp)TiL2, dans lequel :
    I) PI est un ligand de phosphinimine défini par la formule :
    Figure imgb0036
     où N est un atome d'azote ; P est un atome de phosphore ; chaque R1 est un adamantyle non substitué, ou un adamantyle substitué ; et R1'est choisi dans le groupe constitué d'un adamantyle non substitué, d'un adamantyle substitué et d'un hydrocarbyle en C1 à C6 ;
    II) Cp est un ligand de type cyclopentadiényle comprenant un cycle de carbone à 5 chaînons présentant une liaison délocalisée à l'intérieur du cycle et lié à Ti, lequel cycle est non substitué ou peut être substitué davantage ;
    III) chaque L est un ligand activable ; et
    IV) Ti est le titane, et
    B) un activateur.
  9. Système de catalyseur de polymérisation d'oléfine selon la revendication 8 dans lequel l'activateur est choisi dans le groupe constitué d'un aluminoxane ; d'un composé d'organoaluminium ; d'un activateur ionique ; et de mélanges de ceux-ci.
  10. Système de catalyseur de polymérisation d'oléfine selon la revendication 8 ou 9, dans lequel R1'est un adamantyle non substitué ou un adamantyle substitué.
  11. Système de catalyseur de polymérisation d'oléfine selon la revendication 8 ou 9, dans lequel R1'est un adamantyle non substitué.
  12. Système catalyseur de polymérisation d'oléfines selon l'une quelconque des revendications 8 à 11, dans lequel chaque R1 est un adamantyle non substitué.
  13. Système de catalyseur de polymérisation d'oléfines selon la revendication 12, dans lequel R1'et chaque R1 est un 1-adamantyle.
  14. Système de catalyseur de polymérisation d'oléfines selon l'une quelconque des revendications 8 à 13, dans lequel Cp est un (pentaméthyl)cyclopentadiényle.
  15. Système de catalyseur de polymérisation d'oléfines selon l'une quelconque des revendications 8 à 13, dans lequel Cp est un cyclopentadiényle.
  16. Procédé de polymérisation d'oléfines comprenant la mise en contact d'une ou plusieurs parmi de l'éthylène et des alpha-oléfines en C3 à C10 avec le système de catalyseur de polymérisation d'oléfines selon l'une quelconque des revendications 8 à 15 dans des conditions de polymérisation.
  17. Procédé selon la revendication 16, dans lequel lesdits un ou plusieurs parmi l'éthylène et les alpha-oléfines en C3 à C10 consistent en a) de l'éthylène ; et b) une ou plusieurs oléfines choisies dans le groupe constitué de 1-butène ; de 1-hexène ; et de 1-octène.
  18. Procédé de (co)polymérisation d'éthylène comprenant les étapes consistant à :
    A) préparer une première solution de polymère par polymérisation d'éthylène, facultativement avec une ou plusieurs alpha-oléfines en C3 à C10, dans un solvant dans un premier réacteur de polymérisation à une température de 80 à 200°C et une pression de 6 895 à 55 160 kPa (1 000 à 8 000 psi) en présence de (i) le complexe selon la revendication 1 ; et (ii) un activateur constitué essentiellement d'un aluminoxane et d'un activateur ionique ; et
    B) faire passer ladite première solution de polymère dans un second réacteur de polymérisation et (co)polymériser de l'éthylène, facultativement avec une ou plusieurs alpha-oléfines en C3-C10, en présence d'un catalyseur de Ziegler-Natta.
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US4588790A (en) 1982-03-24 1986-05-13 Union Carbide Corporation Method for fluidized bed polymerization
US4613484A (en) 1984-11-30 1986-09-23 Phillips Petroleum Company Loop reactor settling leg system for separation of solid polymers and liquid diluent
US5589555A (en) 1991-10-03 1996-12-31 Novacor Chemicals (International) S.A. Control of a solution process for polymerization of ethylene
US5462999A (en) 1993-04-26 1995-10-31 Exxon Chemical Patents Inc. Process for polymerizing monomers in fluidized beds
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